Linear and nonlinear optical properties of some organoxenon derivatives

Avramopoulos, Aggelos; Serrano‐Andrés, Luis; Li, Jiabo; Reis, Heribert; Παπαδόπουλος, Μάνθος Γ.

doi:10.1063/1.2800023

Cited by 16 publications

(11 citation statements)

References 74 publications

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“…These features suggest that NiBDT is very likely to have large NLO properties. 78 Two singlet states have been computed as quasidegenerate at the CASPT2 level ͑4 meV͒ at the planar optimized D 2h geometry, the 1 1 B 1u ͓65%͑b 3u ͒ 1 ͑b 2g ͒ 1 ͔ and 1 1 A g ͓71%͑b 3u ͒ 2 ͑b 2g ͒ 0 −21%͑b 3u ͒ 0 ͑b 2g ͒ 2 ͔ states. Such value is within the expected accuracy of the method, therefore we cannot establish conclusively which one is the ground state.…”

Section: A the Electronic Structure Of Nibdtmentioning

confidence: 99%

“…It has been noted that a structural change, which induces many low-lying excited states, is very likely to lead to very large NLO properties. 78 For completeness, we note that the important consequences of using sulfur containing ligands on the electric properties has been extensively discussed. 87,88 We also considered the effect of substituting one or two H atoms by CH 3 .…”

Section: E the Effect On The Properties Of Changes In The Structure mentioning

confidence: 99%

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Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives

Serrano‐Andrés

Avramopoulos

Li³

et al. 2009

The Journal of Chemical Physics

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Some linear and nonlinear optical (NLO) properties of Ni(SCH)(4) and several of its derivatives have been computed by employing a series of basis sets and a hierarchy of methods (e.g., HF, DFT, coupled cluster, and multiconfigurational techniques). The electronic structure of Ni(SCH)(4) has been also analyzed by using CASSCF/CASPT2, ab initio valence bond, and DFT methods. In particular we discuss how the diradicaloid character (DC) of Ni(SCH)(4) significantly affects its NLO properties. The quasidegeneracy of the two lowest-energy singlet states 1 (1)A(g) and 1 (1)B(1u), the clear DC nature of the former, and the very large number of low-lying states enhance the NLO properties values. These particular features are used to interpret the NLO properties of Ni(SCH)(4). The DC of the considered derivatives has been estimated and correlated with the NLO properties. CASVB computations have shown that the structures with Ni(II) are the dominant ones, while those with Ni(0) and Ni(IV) have negligible weight. The weights of the four diradical structures were discussed in connection with the weight of the structures, where all the electrons are paired. Comparative discussion of the properties of Ni(SCH)(4) with those of tetrathia fulvalene demonstrates the very large effect of Ni on the properties of the Ni-dithiolene derivatives. A similar remarkable effect on the NLO properties is produced by one or two methyl or C(3)S groups. The considered Ni-dithiolene derivatives have exceptionally large NLO properties. This feature in connection with their other physical properties makes them ideal candidates for photonic applications.

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Section: A the Electronic Structure Of Nibdtmentioning

confidence: 99%

Section: E the Effect On The Properties Of Changes In The Structure mentioning

confidence: 99%

Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives

Serrano‐Andrés

Avramopoulos

Li³

et al. 2009

The Journal of Chemical Physics

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“…[39] Substituent effects in the mechanism of mono-substituted acetylene trimerization was studied by means of topological analysis of the electron localization function. [40] Linear and nonlinear optical properties of some organoxenon derivatives containing the C�C unit were investigated by Avramopoulos et al [41] Most of important information on chemistry of acetylene and its derivatives and properties is gathered in monograph by Diederich, Stang and Tykwinski. [42] The purpose of this article is to show the influence of the X substituent on the unit -C�CÀ H and -C�CÀ C�CÀ H in Xsubstituted acetylene and diacetylene, i. e. XAcH and XAcAcH (where Ac = C�C), respectively.…”

Section: Introductionmentioning

confidence: 99%

Changes in Electron Structure of the Triple Bond in Substituted Acetylene and Diacetylene Derivatives

Jabłoński

Krygowski

2020

ChemPhysChem

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The substituent effect is usually considered by means of various Hammett‐like substituent constants and is most often related to aromatic systems. Unlike this, we present results of our research on the influence of 27 substituents spanning a wide range of electronic properties, from strongly electron‐withdrawing to strongly electron‐donating, on the electron structure of X‐substituted acetylenes and diacetylenes – thus the systems which until now have practically not been subject of any deeper studies. It is shown that the interaction through triple bond(s) is associated with a significant advantage of resonance effects and that the substituent effect transmitted by the C≡C−C≡C unit is about half of that transmitted by the C≡C unit alone. Substituent X mainly affects the closest carbon atom by means of proximity effect, hence changes of charge on this atom do not follow any substituent constants. The effect on further carbon atoms is much smaller. The presence of the C≡C−C≡C unit withdraws more charge from X than a triple bond alone, and hinders communication between X and the terminal H atom. Comparison of substituent effects to those present in X‐substituted benzene derivatives shows that the electronic properties of the terminal hydrogen atom in acetylenes and diacetylenes are most similar to the electronic properties of ortho and para hydrogen atoms in X‐substituted benzene derivatives.

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“…[8][9][10][11][12] Recently, experimental evidence was found for the H-Xe bond in HXeCCH and HXeH molecules. [12][13][14] A few groups 1,3,5,[8][9][10]13,15 have been studying these compounds both experimentally and computationally. These compounds exhibit some interesting spectroscopic properties regarding blue shifts of the n H-Ng band.…”

Section: Introductionmentioning

confidence: 99%

Theoretical predictions of the spectroscopic parameters in noble-gas molecules: HXeOH and its complex with water

Cukras

Sadlej

2011

Phys. Chem. Chem. Phys.

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We employ state-of-the-art methods and basis sets to study the effect of inserting the Xe atom into the water molecule and the water dimer on their NMR parameters. Our aim is to obtain predictions for the future experimental investigation of novel xenon complexes by NMR spectroscopy. Properties such as molecular structure and energetics have been studied by supermolecular approaches using HF, MP2, CCSD, CCSD(T) and MP4 methods. The bonding in HXeOH···H(2)O complexes has been analyzed by Symmetry-Adapted Perturbation Theory to provide the intricate insight into the nature of the interaction. We focus on vibrational spectra, NMR shielding and spin-spin coupling constants-experimental signals that reflect the electronic structures of the compounds. The parameters have been calculated at electron-correlated and Dirac-Hartree-Fock relativistic levels. This study has elucidated that the insertion of the Xe atom greatly modifies the NMR properties, including both the electron correlation and relativistic effects, the (129)Xe shielding constants decrease in HXeOH and HXeOH···H(2)O in comparison to Xe atom; the (17)O, as a neighbour of Xe, is deshielded too. The HXeOH···H(2)O complex in its most stable form is stabilized mainly by induction and dispersion energies.

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Linear and nonlinear optical properties of some organoxenon derivatives

Cited by 16 publications

References 74 publications

Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives

Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives

Changes in Electron Structure of the Triple Bond in Substituted Acetylene and Diacetylene Derivatives

Theoretical predictions of the spectroscopic parameters in noble-gas molecules: HXeOH and its complex with water

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